Catalysts and hydrogenation processes using the catalyst



3,004,914 Patented Oct. 17, 1961 United States Patent Oflicc CATALYSTS AND HYDROGENATION PROCESSES This invention relates to new nickel catalysts and to hydrogenation processes using the catalysts.

Commonly, nickel catalysts consists of nickel salts or oxide on a support such as alumina. Such catalysts require activation and the activation of thecatalystis carried out by reducing the salt or oxide to the metal. With a salt such as the nitrate, this is normally a calcination at about 550 C. to convert the nitrate-to nickel oxide followed by reduction in a stream of hydrogen or hydrogen-containing gas. at a temperature of 150 to 600 C.

The present invention is concerned vu'th-a new support for nickel catalysts and according to one aspect of the invention, a catalyst comprises nickel or a nickel compound, for. example a salt or oxide, supported on a base which consists essentially of sepiolite. As with other nickel catalysts, activation is required before use and it is to be understood that the present invention includes the catalyst ineither its inactive or its active form.

Sepiolite is a. commercially available clay "mineral,

which occurs naturally and which can'also be prepared synthetically. It has .the ideal formula and is also known as Meerschaurn. Further information on sepiolite and its properties may be found in Chemistry and Industry of November 16, 1 957, at pages 1492 to I 1495.

The preparation of the catalyst and its activation may be carried out in any convenient manner, the following three methods being merely illustrative.

(a) The catalyst may be prepared on the base by an to'decompo'se the salt; in the case of the nitrate this requires a temperature of about 550 .C., and the nickel will be converted to theoxide. Final-activation by reduction to metallic nickel can be carried out in a stream of hydrogen or hydrogen-containing gas at a temperature of 150 to 600 C. Sepiolite possesses an advantage over somecommonly used bases-e.g. alumina, in that there is no reaction of the nickel salt with sepiolite during the' heating of the catalyst to reduce the nickel nitrate to oxide, and the final reduction can be carried out at a lower temperature than that necessary for nickel-alumina catalysts. No'damage results to the sepiolite however, if it is heated at a temperature above 600 C.

(b) The catalyst may be prepared by milling dry nickel formate with powdered sepiolite, and the mixture subsequently pelleted.- The advantage of this method of preparation is that a salt such as nickel formate reduces directly to nickel (without going through the oxide state) in a non-oxidising atmosphere, for example in an inert gas stream at a temperature of 150 to 300 C.,

preferably about 250 C. This method has the advantage that it is not necessary to'heat large quantities of catalysts to temperatures of 500 C. and higher. I

(c) The catalystmay be prepared by a technique which utilises the water soluble complex nickel ammine formate Ni(NH (HCOO) which is formed when nickel formate dissolves in ammonia, this complex breaks down on heating to give nickel formate again. By using this water-soluble complex catalysts may be prepared by the impregnation technique from normally water insoluble compounds such as nickel formate. To prepare a catalyst by this method nickel formate is dissolved in ammonia solution, and the solution used for the impreg nation of sepiolite granules or pellets. The catalyst is then dried, and activation is carried out by the method described under (b). In all the preparations, it may be desirable to calcine the sepiolite prior to incorporating the nickel compound. A convenient calcination temperature is about 550 C.

After the reduction, the nickel catalyst should not be allowed to come'into contact with air or spontaneous oxidation of the nickel to nickel'oxide may'occur.

Preferably the catalyst contains from 1 to 50% of nickel (expressed as elemental nickel) by weight of total catalyst, and more particularly from 5 to 15% wt.

The new catalyst described above may be used in a process which also constitutes part of the invention, namely a process for the hydrogenation of organic compounds which comprises contacting the compound or compounds, together with hydrogen, with a catalyst comprising nickel supported on a base as hereinbefore described, under conditions of temperature and pressure which favour hydrogenation.

The process of this invention is suitable for usein the treatment of an organic compound containing a carbon to carbon double bond in the molecule for the saturation of this bond; The process may also be employed for the treatment of an organic compound containing a carbon to carbon triple bond in the molecule for the conversion of this bondto a carbon to carbon double'bond or for the saturation of the bond. Also the process may be employed fo'rthe conversion of arcmatic compounds to naphthenic compounds. Preferred feedstocks are hydrocarbon, or petroleum fractions, "or materials consisting largely of hydrocarbon produced from petroleum by any process tar-treatment. The process is of particular value for the conversion of di-olefinie compounds to mono-olefinic compounds. It has been found that under suitable reaction conditions, di-oletinic compounds may b'e converted to mono-olefinic compounds with only'low conversion of these or other mono-olefinie compounds to saturated compounds.

The catalyst is particularlysuitable for the partial hydrogenation of steam cracker gasoline, which is herein defined as a 'gasolineproduced by cracking a petroleum distillate in the presence of steam. Such cracked'gasoline is highly unsaturated and tends to form gum possible due to the presence of styrene, cyclopentadiene and other conjugated dienes. j

A? particularly suitable processin which the catalyst may be used is a method for improving a gasoline containing di-olefins and/orstyrenes and also in certain cases cyclenes and alkenes, for example a'steam cracker gasoline. 'Ihe gasolineis passed with hydrogen, or a gas mixture containing hydrogen, over a catalyst consisting of nickel deposited on a catalyst base,'as.hereinbefore deample a platformer tailgasfjS uitablya gas employee containing 70 mol percent at hyd gen, A yp a will consist of 70 mol percent of hydrogen and 30 mol percent of C1 to C4 paraffins. Other suitable gases are steam cracker tail gas, cataly ic cracker; cashe i gas en' d fr m idehvd ex mtien o hyd o rbo Preferably the severity of the conditions of hydrogenaon i lected to. provide. a high pe ee t geconversion of y releiinsp e ntt one-olefins and of any s yr n preseht to saturated hydrocarbons. As W911. known in t a t. severity oi hydrog nation can be increa e y rai i g h yd ogen par ialpressur raisin t e re io temperature, increas g. the hyd en/ eds k ratio or decreasing the flow rate. H V

The h drogen consumption per unit. weight of feed tock a measure of. the egree o u on oi vth diolefin's andstyrenes, and hence the degree of'lmprovemeat in the gum: st bility oi t e gas in Pr t rably th hydrogen consumption is at least 60 s.c.f./b., and more particularly at least 120 -s .c. f./b., and it may be more .th-an-1-50 s.c.fy.j/b. The upper limit of hydrogen, con- Temperature 7 80to1'80CJ. Pressure 0 to 1000 p.s.-i.'g. (prefer- V v ablYZOO-BOO p.s.'i. g.). Gas recycle rate (recycle or once through) 300 to 1000 -s.c.'f./b. of 7 hydrogen. g "Space-velocity; ;;ne e 0.5 to 10 v./v.hr. (prefere 1ably' about 2 v-./v./hr.).

The treated gasoline may be. stabilised to give a product of low Q content and may also be re-run to remove a small proportion of heavy ends. Re-running at a maxi mum temperature. of not'm ore than 400' F. may be advisable, since high rc-running temperatures can adversely fect s stabilitw Suitable tests which give a measure of the stability of gasolines duringstoragc orin an engine are. the Induction Period test '(A STM Method D5 2,5515)., the Accelerated Gumflest (13873449), and the Existent Gum (ASTM Method 11381-57). I L 7 The invention .isillustrated by the following examples:

7 v :1 Preparation of catalyst as in method (0) described above 180 .g. of 6-410 1388 mesh sepiolite were imp gn ed with a solution of 77.5 g. analar nickel nitrate 1 dissolved in 200 distilled water. tlhe solution was absorbed. The material was dricd' at 100 C. .for 1 hr. and then roasted at 550 6. for -2 -hrs. in air to' give a catalyst of nickel oxide on-vsepiolite.

V M LE 2 Preparation 0) catalyst as in method (b) described above 400 'g. of 304510 BSS mesh sepiolitc was ball milled in the dry state with 1 22 g. of nickel formate for 3 The resulting nickel 'formate-sepiolite mixture was then pelleted to x Va'f pellets. 7 j

, Ircparatioiz of. cgztalys't as in mgtliod ic) described above 200 ml. 87 g.) at sepiolit e. crushed to 6-l0mesh and to 200 C. (preferably V roasted for 2 at 0- C. were impregnated with a solution of 29 g. nickel formate, Ni(HCO .2H O, in 80 ml. ammonia solution (S.G. 880) and 20 ml. distilled water. All the solution was absorbed. The catalyst was dried in a current of air at 100 C. for 3 hrs. The nominal nickel content was 9.6% wt.

EXAMPLE 4 1 d Specific gravity at F./60 F .7825 ASTM distillation:

IBP v o q C 45.0 7 2% volume recovered at C 57.5 5% volume recovered at C 63.0 10% volume recovered at C 67.5 20% volume recovered at '-C-' 76.0 30% volume recovered at C--. 85.0 40% volume recovered" at .C 94.5 50% volume recovered at C 103.5 60% volume recovered at ....-C 113.0 1 volumerecovered-at-.. :C 122.0 volume recovered at C 133.0 volume recovered at C 155.0 FBP C..- 218 Recoverypercent vol 98.0 Residue do 1.1

Loss 7 a do 09 Recovered at 70 C do 12.5 Recovered at 10 C";; c;.. do 46.0 Recovered at 140 C do 83.5 Gum existent n ma /1OO ml 8 Gum accelerated (1.20 min.).. mg./ ml..- 8 Gum accelerated (240 min.) ..mg./ 100 1111 227 Induction period ASTM ..rnin' 2'90 Induction period I? Y ..r nin 225 'Bromine number 65.8 Sulphurn percent wt-.. 0.005 Research octane number {clear v 93.8

Pure hydrogen gaswas used on a once through basis.

50 manna: .2

Catalyst Nickel on Nickel on i seplolite .Timeionstream s-itnos' 8-14 HOS Temperature; 99.4 100.6 essure.. .s.l.g..- .201. 202 Space velocity -y./v.lhr-; 2. 2 Hydrogen absorption in s.c.t./b 220 Catalyst bulk densities. gJml--. 1. 1 0. 78

It will be seentrom thetaole that the nickel-on-sepiolite catalyst had ag-rea'ter activity for hydrogenation (as shown by the hydrogen absorption figureslthanjthe nickel .on alumina catalyst. 'Thenickel-on-sepiolite catalyst also has a lower bulk density than the nickel-onalumina catalyst .so that on a weight basis the difference would be even more marked. f a

1 EXAMPLE 5 v V Powdered sepiolite, of 30-60 mesh grain size was cal- .cined -for -2 hours at 550 C.,, and mixed with 1 percent weight. powdered graphite to givc an even graphite distribution. The mixture was then-pelleted to /a x A! cylinders. The sepiolite pellets were contacted with a solution of the complex -Ni: (NH3)51(iHtQOO,-)2 such that the resultant nominal nickel content of the impregnated pellets was 10 percent weight. All the solution was absorbed by the sepiolite pellets which were then air dried at 100 C. The catalyst had a bulk density of 1.05 g./ml.

EXAMPLE 6 The catalyst of Example was activated by heating for 2 hours at atmospheric pressure and 250 C. in a stream of hydrogen. The hydrogen flow rate was 100 v./v./hr. It was then tested for hydrogenation activity using a steam cracker gasoline as feedstock. Inspection data on the feedstock are given in Table 3 overleaf.

TABLE 3.INSPECTION DATA ON STEAM CRACKER GASOLINE FEEDSTOCK Specific gravity at 60 F./60 F 0.7800

ASTM distillation test:

IBP C 44.5 2% recovered at C 53.5 5% recovered at C 60.5 recovered at C 66.5 20% recovered at C 76.0 30% recovered at C 85.0 40% recovered at C 95.0 50% recovered at C 105.0 60% recovered at C 113.5 70% recovered at C 122.5 80% recovered at C 135.0 90% recovered at C 158.5 FBP C 214.0 Recovery percent vol 97.5 Residue do 1.3 Loss do 1.2 Recovered at 70 C do 13.5 Recovered at 100C do 45.0 Recovered at 140 C do 82.5 Total sulphur cpercent weight" 0.007 Gum existent mg./ 100 ml *(22)4 Gum accelerated (120 minute), mg./ 100 ml- *(28)25 Gum accelerated (240 minute), mg./ 100 ml- *(137) 113 315 Induction period ASTM min Induction period IP min 235 Bromine number 70.0 Diene index 4.44

Figures in parentheses indicate gum content before washing with n-heptane.

The hydrogenation was carried out for a 6 hour period under the -following conditions:

The hydrogen absorption, a measure of the catalyst activity, was 210 s.c.f./b. Inspection data on the product were as follows:

6 Specific gravity 0.7785 Gum existent Mg./ Ml. *1 Gum accelerated minute) Mg./ 100 lvfl. *1 Induction period (ASTM) min 720 Bromine number 42.7

* After washing with n-heptane.

These figures show the considerable improvement in existent and accelerated gum figures and in the induction period resulting from the hydrogenation.

I claim:

1. A catalyst comprising a member of the group consisting of nickel and nickel compounds supported on a base consisting essentially of sepiolite.

2. A catalyst as claimed in claim 1 having a nickel content, expressed as elemental nickel of from 1 to 50%, by weight of total catalyst.

3. A catalyst as claimed in claim 2 having a nickel content, expressed as elemental nickel, of from 5 to 15% by weight of total catalyst.

4. A process 'for the hydrogenation of organic compounds comprising contacting the compounds together with a catalyst comprising nickel supported on a base consisting essentially of sepiolite.

5. A process as claimed in claim 4 wherein the compounds are derived from petroleum.

6. A process as claimed in claim 5 which is a process for improving the gum-forming tendency of gasolines containing at least one compound selected from the class consisting of di-olefins and styrenes.

7. A process as claimed in claim 5 wherein the gasoline is a steam cracker gasoline.

8. A process as claimed in claim 6 wherein the research octane number (with 1.5 ml. TEL/IG) of the product is not less than the research octane number (with 1.5 ml. TEL/1G) of the feedstock.

9. A process as claimed in claim 6 wherein the temperature is 0-200 C. and the pressure is 0-1000 p.s.i.-g.

10. A process as claimed in claim 9 wherein the temperature is 80-180 C. and the pressure is 200-300 p.s.1.g.

11. A process as claimed in claim 9 wherein the gas rate is 300-1000 s.c. f./b. and the space velocity is 0.5-10 v./v./hr.

References Cited in the file of this patent UNITED STATES PATENTS 2,042,298 Davis May 28, 1936 2,073,578 Guynn Mar. 9, 1937 2,116,061 Dorrer May 3, 1938 2,542,471 Brandon Feb. 20, 1951 2,638,438 Hoffman et al. May 12, 1953 2,735,879 Redcay Feb. 21, 1956 2,865,851 Porter Dec. 23, 1958 2,901,423 Herbert et a1. Aug. 25, 1959 UNITED STATES PYATENTOFFICE CERTIFICATE OF CORRECTION Patent No. 3304 914 October l7 1961 Peter Thomas White error appears in the above numbered pat- It is hereby certified that t the said Letters Patent should read as ent requiring correction and the corrected below.

Column l line 13,, for "consists" read consist column 2 lines56 and 57, for "possible" read possibly column 4, line 34, for "10 0" read 100 c line e'z iw 8" read 46 Signed and sealed this 10th day of April 1962.,

(SEAL) Attest:

ERNEST w; 'swiosmg DAVID L. LADD Attesting Officer Commissioner of Patents 

1. A CATALYST COMPRISING A MEMBER OF THE GROUP CONSISTING OF NICKEL AND NICKEL COMPOUNDS SUPPORTED ON A BASE CONSISTING ESSENTIALLY OF SEPIOLITE.
 4. A PROCESS FOR THE HYDROGENATION OF ORGANIC COMPOUNDS COMPRISING CONTACTING THE COMPOUNDS TOGETHER WITH A CATALYST COMPRISING NICKEL SUPPORTED ON A BASE CONSISTING ESSENTIALLY OF SEPIOLITE. 